Comprehension-1

Thermochemistry is related with heat change in a chemical reaction. Heat change at constant
volume given as U & at constant pressure given as H .By I.U.P.A.C. sign convension
For endothermic reaction : H 0; U 0
For exothermic reaction : H 0; U 0
1. Standard Enthalpy of formation (H 0f ) :-Enthalpy change on formation of 1 mole substance
from its elements when all are in their standard state.
Assumption taken: For elements in their standard state H 0f 0
Ex- C(graphite)+O2 ( g ) CO2 ( g ); r H H 0f (CO2 )
0
0
Here, H f [C ( graphite)] H f [O2 ( g )] 0

2. Standard Enthalpy of reaction ( r H 0 ) :

r H iP H 0f ( products) iR H 0f (reac tan ts)

0
3. Standard Enthalpy of neutralisation ( H neut
. ) :-Enthalpy change on complete neutralisation

of 1 gram equivalence of acid/base.

CASE-I:- In case of neutralisation of S.A./S.B. with S.B./S.A.
0
H (aq) HO (aq) H 2O(l ); H neut
. 57.1KJ / eq 13.7 KCal./ eq

CASE-II:- In case of neutralisation if one or both are weak.

0
H neut
. 57.1KJ / eq (Hydration energy is not included)

LAWS OF THERMOCHEMISTRY
1. Lavoisier & Laplace law:- The law states that the heat evolved in a chemical reaction is
equal to the heat absorbed when the reaction is reversed.
C(s) O2(g)
CO2(g) ; H=-94.3 Kcal

CO2 (g)
C(g) O2 (g) ; H = + 94.3 Kcal
2. Hesss law of constant heat summation:- The law states that at constant pressure the
total enthalpy change accompanying a chemical reaction is the same whether the
reaction takes place in one or more steps .This shows that ENTHALPY is a state function
& is extensive property.
H 3 z
H1 x
H 2 y
A

B
C

D
& A D; r H ?

By Hesss law r H x y z
Q.1

Diborane is a potential rocket fuel which undergoes combustion according to the reaction,
B2H6(g) + 3O2(g) B2O3(s) + 3H2O(g)
From the following data, calculate the enthalpy change for the combustion of diborane :
2B(s) + O2(g) B2O3(s) ;
H = 1273 kJ
H2(g) + O2(g) H2O(l) ;

H = 286 kJ

H2O(l) H2O(g) ;

H = 44 kJ

2B(s) + 3H2(g) B2H6(g) ;

H = 36 kJ

[JEE 2000]

Ans. 2035kJ mol1

Q.2

Q.3

Which of the following reactions defines H 0f ?

(A) C(diamond) + O2(g) CO2(g)

(B*) 1/2 H2(g) + 1/2 F2(g) HF(g)

(C) N2(g) + 3H2(g) 2NH3

(D) CO(g) + 1/2O2(g) CO2(g)

H 0f for CO2(g), CO(g) and H2O(g) are 393.5, 110.5 and 241.8 kJ mol1 respectively. The
standard enthalpy change (in kJ) for the reaction
CO2(g) + H2(g) CO(g) + H2O (g) is
(A) 524.1
(B*) 41.2
(C) 262.5

Q.4

[JEE 2003]

(D) 41.2

Which of the following is not an endothermic reaction?

(A*) Combustion of methane
(B) Decomposition of water
(C) Dehydrogenation of ethene to ethylene
(D) Conversion of graphite to diamond

[JEE 2000]

[JEE 1999]

Q.5

For the allotropic change represented by the equation C (graphite) C (diamond), H =

1.9 kJ. If 6 g of diamond and 6 g of graphite are separately burnt to yield CO2, the enthalpy
liberated in first case is
(A) less than in the second case by 1.9 kJ
(B) more than in the second case by 11.4 kJ
(C*) more than in the second case by 0.95 kJ
(D) less than in the second case by 11.4 KJ

Q.6

NH3(g) + 3Cl2(g) NCl3(g) + 3HCl (g); H1

N2(g) + 3H2(g) 2NH3(g); H2
H2(g) + Cl2(g) 2HCl (g) ; H3

The enthalpy of formation of NCl3 (g) in the terms of H1, H2 and H3 is

H 2 3
H 3
2
2
H 2 3
H 3
(C) H f H1
2
2
(A*) H f H1

Q.7

(B) H f H1

H 2 3
H 3
2
2

(D) None

Ethanol can undergoes decomposition to form two sets of products

C2H5OH (g)

if the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the enthalpy
involved in the decomposition of 1 mole of ethanol is
(A) 65.98 kJ
(B*) 48.137 kJ
(C) 48.46 kJ
(D) 57.22 kJ

Q.8

Hydrazine, a component of rocket fuel, undergoes combustion to yield N2 and H2O.

N2H4 (l) + O2 (g) N2 (g) + 2H2O (l)

What is the enthalpy combustion of N2H4 (kJ/mole)
Given Reaction

2NH3 (g) + 3N2O (g) 4N2 (g) + 3H2O (l)

N2O (g) + 3H2 (g) N2H4 (l) + H2O (l)
4NH3 (g) + O2 (g) 2N2H4 (l) + 2H2O (l)
H2 (g) +

1
O (g) H2O (l)
2 2

(A*) 620.5
Q.9

H/kJ
1011 kJ
317 kJ
286 kJ
285 kJ

(B) 622.75

(C) 1167.5

(D) + 622.75

Find rU for the reaction 4HCl (g) + O2 (g) 2Cl2(g) + 2H2O (g) at 300 K. Assume all
gases are ideal.
0
r H 300
Given: H2(g) + Cl2(g) 2HCl (g)
K = 184.5 kJ/mole
2H2(g) +

1
O (g) 2H2O (g)
2 2

0
r H 300
K = 483 kJ/mole

(Use R = 8.3 J/mole)

(A) 111.5 kJ/mole
Q.10

(B) 109.01 kJ/mole

(C*) 111.5 kJ/mole

(D) None

The enthalpy changes of the following reactions at 27C are

Na(s) +

1
Cl (g) NaCl (s)
2 2

H2(g) + S (s) + 2O2 (g) H2SO4 (l)

rH = 411 kJ/mol
rH = 811 kJ/mol

2Na(s) + S(s) + 2O2 (g) Na2SO4 (s) rH = 1382 kJ/mol

1
1
H2(g) + Cl2(g) HCl (g)
2
2

rH = 92 kJ/mol;

R = 8.3 J/K-mol

from these data, the heat change of reaction at constant volume ( in kJ/mol) at 27C for the
process
2NaCl (s) + H2SO4 (l) Na2SO4 (s) + 2HCl (g) is
(A) 67
(B*) 62.02
(C) 71.98
(D) None